Preparation of hydrogenated polymers



Dec. 15, 1959 R. L. coBB Erm.

PREPARATION 0F HYDROGENATED POLYMERS Filed March 11, 1957 INVENTORS, C. R. SCOTT A TTORNEYS RAYMOND L. COBB BY ZOCJOW mm rJOn.)

United States Patent Oiiice 2,917,495 Patented Dec. 15, 1959 PREPARATION oF HYDROGENATED PoLYMERs Raymond L. Cobb, Bartlesville, Okla., and Cleveland Rex Scott, East Providence, RJ., assignors to Phillips Petroleum Company, a corporation of Delaware Application March 11, 1957, Serial N0. 645,376

10 Claims. (Cl. Mtl-85.1)

This invention relates to a method for the preparation of hydrogenated rubbery polymers in a finely subdivided form. In one aspect, the invention relates to the preparation of rubbery polybutadienes having a small uniform particle size.

It is an object of this invention to provide hydrogenated rubbery polymers in a more desirable form.

Another object of this invention is to provide an improved method for the preparation of lnely sub-divided hydrogenated rubbery polymers.

Still another object of this invention is to provide an improved method for the preparation of hydrogenated polymers of butadienes and copolymers of butadiene and styrene having a small uniform particle size.

These and other objects of the invention will become more readily apparent from the following detailed description and discussion.

The foregoing objects are achieved broadly by dissolving a hydrogenated rubbery polymer in a solvent, emulsifying the resulting solution with water and an emulsifying agent, removing the .solvent from the emulsion by vaporization and breaking the emulsion by ntroducing the emulsion into a water-soluble polar organic precipitating agent with a minimum of agitation.

' In one aspect of the invention, the emulsion is broken by introducing the emulsion onto the surface of waterlsoluble polar organic precipitating agent with a minimum fof agitation.

This process is applicable for producing small particle hydrogenated polymer in the size range of between about 1 and about 20 microns from hydrogenated rubbery polyaners containing from to 50 and preferably from 0 yto 20 percent unsaturation based on 100 percent theoretical unsaturation for the unhydrogenated rubbery polymer.

The polymers treated in the method of this invention :are selected from homopolymers of dienes and copolymers of styrene and butadiene, using not over about 30 parts of styrene by weight. The polymers are prepared by emulsion polymerization at a temperature of 5 to 140 .F. and preferably at a temperature within the range of 20 to 60 F. A very good balance of polymer properties is obtained by polymerizing butadiene at a temperature of about 41 F.

Hydrogenation of the polymers is carried out in the presence of a hydrogenation catalyst such as, for example, nickel, kieselguhr, Raney nickel, copper chromite, molybdenum sulfide, metallic platinum, palladium, etc. at elevated temperatures, preferably in the range of 300 to 600 F. and at pressures up to 3000 p.s.i.g. Prefer! ably nickel kieselguhr is used as the catalyst and the reaction is carried out over a time period in the range of l to 24 hours, and preferably between about 2 and about 8 hours.

For a more detailed discussion of the polymers and the methods for hydrogenating same, reference is had to the copending application of R. V. Jones, Serial No.

395,291, tiled November 30, 1953, now Patent No. 2,864,809.

In carrying out the process of this invention, the first step comprises dissolving the hydrogenated rubbery polymer in a solvent material. The preferred solvents for this purpose are those boiling in the range between about 50 and about 150 C.; however any solvent that can be satisfactorily removed from subsequently formed emulsions without causing softening of the rubbery polymer can be employed. Since the solvent is removed from the rubbery polymer-water solvent emulsion in a later stage, usually by vaporization, solvents which form minimum boiling azeotropes with Water are particularly suitable. Typical solvents which can be employed in the process are cyclohexane, methylcyclohexane, benzene, toluene, isooctane and carbon tetrachloride. It is preferred that suliicientsolvent be employed to provide a solution containing about 10 percent polymer by weight or less. However, if desired, solutions of higher polymer concentration can be employed.

Emulsication of the rubbery polymer solution is carried out in the presence of water and an emulsifying agent. It is desirable that the water be present in an amount comprising at least 30 percent by weight of the solution of hydrogenated rubbery polymer and a preferred upper limit for the amount of water to be used is about 5 times the quantity of water by weight` as the polymer solution present. ln any case, it is desirable that suiicient water be present to establish a continuous water phase. As inthe case ofthe solvent material employed, it is necessary toefect separation of the water from the final polymer product. Therefore, l.although larger amountsV of water Vcan be used, it is desirable that the operation be carried out with the minimum quantity of water which is feasible. The emulsication process is carried out by agitating the mixture of polymer solution, water and emulsifying agent, the desired agitation being provided in any conventional manner, such as, by stirring or other conventional means.` It is necessary inorder to obtain the desired end product that the emulsiiication step be carried out at a temperature below the softening point of the hydrogenated rubbery polymer. A suitable temperature usually lies in the range of from about F. to about F.

The emulsifying agents used in this portion of the process comprise in general oill soluble emulsifying agents, examples of which include fatty acid esters of polyhydric alcohols or of ether alcohols, for example, glycerol mono-stearate; esters of ethylene glycol, diand tri-ethylene glycol and polyethylene glycol, for example, the condensation product of oleic acid with 6 mols of ethylene oxide; fatty esters of sugar alcohols; alkyl urethans; fatty amides of monoethanolamines; fatty nitriles and fatty acid amides, such as oleic morpholide. The emulsifying agent used can be added to either the polymer solution or the water, or it can be formed during the emulsifying step. As an example of the latter type of operation, morpholine is added to the water, oleicacid is dissolved in the polymer solution and the two phases are then brought into contact to form a fatty acid morpholide emulsifying agent in admixture with water and the hydrogenated rubbery polymer.

The amount of emulsier employed is generally at least about 5 parts by weight per 100 parts by Weight of rubbery hydrogenated polymer solution. However, the amount will vary depending on the particular emulsitier employed and the particular polymer to be emulsied. Y

Afterl the emulsion is prepared, the solvent is removed therefrom by vaporization. Various methods can be employed for carrying out this operation, such as stripping, distillation, etc. A suitable method for removing the solvent is to distill olf this material from the emulsion while simultaneously stirring or agitating the liquid. The solvent removal step also is carried out below the softening point of the hydrogenated `rubbery polymer. "Ihe temperature of this operation can be kept at a minimum boiling azeotrope with water, or *by reducing the pressure under which distillation or stripping is carried out, vor by a combination of the two methods. The latter method, namely reduction of pressure, is particularly desirable jin that it serves to increase the ,relative volatility of lthe solvent, since ,the vapor pressure :of .water does not change rapidly with changes in pressure.

Following the solvent removal operation, the polymerwater emulsion is broken, to precipitate :the polymer in the form of the desired small uniform particles. .'It:has been found preferable to perform this .operation .at substantially normal atmospheric temperatures, that is, about 60 .to 80 F. Thus, if the solvent removal operation is .carried out at a temperature above this, it is desirable that emulsion be allowed to cool Yor be .cooled to atmospheric .temperature before Aproceeding with the breaking operation.

It has been found that the degree-of.subdivision of the product polymer is dependent to a great extent on the amount of agitation .which occurs during the emulsion breaking operation. Thus it has been found desirable to Aintroduce the emulsion into or onto the surface of the emulsion breaking or precipitating agent and this operation should be performed with a minimum of agitation. The dispersion which results is then allowed to stand for several seconds, usually at least tive seconds, after which the solution can be agitated to effect complete dispersion of the polymer in the precipitating agent-water mixture.

Suitable precipitating agents which can be used in this operation linclude alkyl alcohols and alkyl ketones, the alkyl vgroup containing up to five carbon atoms in the alcohols and up to three carbon atoms in the ketones, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, etc., and ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, etc. Another group of precipitating agents are the amines such as pyridine and alkylamines tontaining un to ve carbon atoms. including diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, dibutylamine, tertiary-butylamine, secondarybutylamine, amylamine, isoamylamine, tertiary-amylamine, etc. The amount of precipitating agent used usually is between about and about l0 parts by weight per part by `weight of 4water present in the water-polymer emulsion. If desired, however, greater quantities of precipitating agent can be used.

Following the emusion breaking step, the dispersed polymer particles are recovered by a suitable separation means, such as by filtration, followed by a conventional drying operation.

The `small particle hydrogenated rubbery polymer prepared vby the method of this invention linds use particularly as a molding powder. Since the hydrogenated rubbery polymers are thermoplastic in nature, molds can be easily lled with the small particle material and heated to form a molded object. If desired, small amounts of such filler materials as gelatin and talc can be added t0 the water .prior to emulsifying the water with the hydrogenated polymer solution.

In order to more fully described the invention and vprovide aqbetter understanding thereof, reference is .had to the accompanying drawing which is a diagrammatic illustration in cross-section of apparatus suitable for carrying out the method lof the invention. Referring to the drawing, a hydrogenated rubbery polymer, such as polybutadiene, is introduced 'to polymer solution vessel 8, through conduit 2. Simultaneously, a hydrocarbon solvent, for example, cyclohexane, and a fatty acid m01'- pholide emulsifying agent are introduced 'to the same .4 vessel through conduits 4 and 6, respectively. The polymer solution vessel is equipped with a stirrer 12 to agitate the mixture and is also provided with a steam heating coil so that the temperature within this vessel can be maintained at the desired level. When the polymer is placed in solution, a mixture ofpolymer in solution and emulsifying agent is removed from the bottom of vessel 8 through conduit 14 and introduced to emulsitier 16. At the same time, water is also introduced to the emulsiiier through conduit 32. The latter vessel is also equipped with a mixer 13 and a steam coil 20 for suitably agitating the mixture contained therein and providing the desired emulsifying temperature. In the event that the temperature employed in the emulsilier approaches the vaporzation temperature of the solvent, a cooling coil 23 is provided in the upper portion of the emulsiiier to condense such solvent, which is then returned to the emulsion.

' Emulsion is withdrawn from the emulsilier through conduit 34 and passed through cooler 36 wherein the temperature `is reduced to substantially atmospheric. Following this, the emulsion is introduced to stripper 40. Control of the temperature of the material in the stripper is provided by a by-pass 38 around cooler 36. In the event that the emulsicationis carried out at atmospheric `temperature, the Ventireiemulsion yielded from this vessel Acan be by-.passed through conduit 38. The temperature in stripper 40 is elevated to a sufficient level by `steam introduced :to reboiler 43 whereby the solvent cyclohexane is vaporizedfrom the emulsion,.said solvent passing Yoverneadtrom .trie stripper through conduit 42. The remaining emulsion, now comprising ,polymer and water, .passes from thebottom of stripper .through .conduit 44 and is introduced to emulsion .breaker 46, .being owed onto ythe surface of a liquid precipitating agentmaintainedtherein. After'a several seconds delay, precipitated hydrogenated rubbery polymer is dispersed :in the emulsion breaker by means .of Vstirrer 48. Since a `time delay before the dispersion step is desirable, emulsion vbreaking 46 in a continuous operation, comprises a plurality of emulsion breaking vessels.

A slurry or' finely sub-divided hydrogenated polymer in water and .emulsion breaking agent, is passed from vessel 46 through conduit 50to filter 52 wherein the yolymer particles are filtered from the liquid, the latter .naterial being discharged from the lter through conduit 54. The particles of rubbery polymer containing residual water and emulsion breaker are then passed through conduit 56 and dryer 58, emerging therefrom through conduit 62 as dry product. The residual water and emulsion breaker exit from the drier via conduit 6l) for further treatment as desired.

Although the method illustrated by the accompanying drawing represents the preferred embodiment of the invention, it is not intended that it be taken in any limiting sense and ythat other operating steps and procedures can be used within the scope of the invention. Thus, for example, referring to the figure, if it is desired to form an oil soluble emulsifying agent in situ, such as, for example by the reaction of morpholine and oleic acid to form a fatty acid morpholide, this can be accomplished by introducing the oleic acid to the polymer solution tank Y8, and by dissolving morpholine in water in aqueous solution tank 26, the latter materials being introduced to tank 26 through conduits 22 and 24 respectively. The desired emulsion is obtained when the polymer solution and aqueous solution of morpholine are introduced to the emulsifier through conduits 14 and 32, respectively.

As previously stated, removal of the solvent by vaporization can be effected in any conventional manner, as can also the steps of filtration and drying to provide the final finely divided uniform polymer product.

The following examples are presented as illustrative of the'process Of this' invention.

n y EXAMPLE I y Hydrogen'ated rubbery polybutadiene of small particle `size was prepared by the following procedure.

Rubbery polybutadiene was prepared by emulsion polymerization according to the following recipe.

Polymerization Recipe and 3 contained (as ingredients) the amounts of methanol (as rinse) and KOH shown above. Run 1 contained as an ingredient 0.30 part methanol (as rinse) and 0.03 part KOH on the same basis as given above.

Polymerization data Parts by Polymeri- Mooney Run Weight zation Polymeri- Conver-- Viscosity N o. Tert- Temp., zaton sion, iter Dodecyl F. Temp. Percent Venting Mercaptan (ML-4) 0. 48 41 16 59 18 0.48 4l 14. l 60 18 0. 42 41 V21 61 25 A blend of latex containing 32.8 weight percent of latex from run l, 35.6 weight percent of latex from run 2, and 31.6 weight percent of latex from run 3 was then made up. This latex blend was then shock coagulated by adding it to isopropyl alcohol. The serum was then drained, `and the crumb was given three 15- minute water washes at 130 F. (The Mooney viscosity of this polymer was 20 (MLP-4).)

The polybutadiene rubber, prepared as described above, was hydrogenated by the following procedure. Seventysix grams of nickel-kieselguhr catalyst, prepared by reducing nickel hydroxide impregnated kieselgihr in hydrogen at 775 F. for 4 hours, was rinsed into the hydrogenation reactor with 2 liters of methylcyclohexane. The reactor temperature was then raised to 300 F., and a solution of 800 grams of the rubbery polybutadiene dissolved in 7 liters of methylcyclohexane was pumped into the reactor. This charge was followed by rinse of 2 liters of methylcyclohexane. The reactor was then heated to 450 F., and hydrogen was pressured into the reactor until the pressure reached 500 p.s.i.g. The hydrogenation reaction was carried out for 3 hours, during which time the hydrogen feed was adjusted to maintain the reactor at 500 p.s.i.g.- At the end of 3 hours, the reactor contents were blown down into methylcyclohexane, yielding a solution of hydrogenated rubbery polybutadiene which contained approximately 4 percent by weight hydrogenated polymer. The solution was then centrifuged and passed between the coils of a magnet, these two steps serving to remove the catalyst present. A sample of the solution was evaporated to recover the hydrogenated polymer, and this hydrogenated polymer was found to contain approximately 8 percent unsaturation based on the original unsaturation.

A number of hydrogenation runs were made, using device.

. 6 essentially the same procedure as given above in which the above described rubbery polybutadiene was hydrogenated. The solutions of hydrogenated polymer in methylcyclohexane from seven different hydrogenation runs were blended to yield a solution of hydrogenated rubbery polybutadiene in methylcyclohexane which contained approximately 4 percent by weight of the hydrogenated polymer. The hydrogenated polymer in this blended solution contained approximately 7-8 percent unsaturation based on the unsaturation present in the original polybutadiene rubber.

The hydrogenated rubbery polybutadiene present in the above described solution was precipitated in the form of Very fine particles by the following procedure.

Two hundred iftycubic centimeters of water and four grams of morpholine were combined and heated to about C. Four grams of oleic acid and one hundred grams of the above-described solution of hydrogenated rubbery polybutadiene in methylcyclohexane were mixed and heated until complete solution was effected, after which `this solution was added to the aqueous solution of morpholine. The resulting mixture was stirred at the reflux temperature of the methylcyclohexane-water azeotrope (81 C.) for l5 minutes. This was carried out in a flask which was fitted with a reflux condenser so that the methylcyclohexane and water which was evaporated was condensed and returned to the flask. The emulsion resulting lwas then placed under a partial vacuum, and gradually decreasing temperature (starting at 81 C.) and continuous stirring, the methylcyclohexane was stripped off. The majority of the methylcyclohexane distilled 01T between 65 and 80 C. After about two hours, the resulting emulsion was cooled to room temperature and broken by pouring in several increments into three liters of methyl alcohol. The hydrogenated polymer precipitated as line particle. After about ten seconds, the solution was stirred and the solid product was filtered out of the rnethanol-methylcyclohexane mixture, washed three times with methanol, and dried. The yieldv of small particle hydrogenated rubbery polybutadiene was 1.9 grams of a powder which consisted largely of spherical particles in the particle size range between two and ten microns.

EXAMPLE II Three hundred grams of the solution of hydrogenated rubbery polybutadiene in methylcyclohexane, identical to the polymer solution prepared in Example l was treated in the following manner. One hundred eighty grams of the methylcyclohexane was stripped olf of this polymer solution, yielding a rather viscous lacquer. Four grams of morpholine and four grams of oleic acid were then added to the viscous lacquer, after which this viscous lacquer was heated to about 75 C. Two hundred fty cubic centimeters of water, previously heated to 75 C. was then-added with vigorous stirring. The -iirst iifty to seventy-live cubic centimeters of water was added very slowly, and the remainder was poured in quite rapidly. The mixture was stirred rapidly for an additional ve minutes, after which the rate of stirring was decreased to the minimum speed of a standard laboratory stirring The resulting emulsion was then placed under' vacuum, and solvent was evaporated for about six hours. During this evaporation, the temperature was maintainedl at 50-60 C. after the initial drop from 75 C. when the pressure was reduced to strip off the solvent. sion was then stirred very slowly overnight at room temperature, after which the emulsion was broken by pouring into six liters of methanol, using the same procedure described in Example I. The precipitated solid polymer was a fine white powder weighing 9.5 grams. A microscopic examination of the product proved the product toI be in the form of round particles, the majority of which were in the particle size range between four and ten. microns.

7 EXAMPLE ,HI

`Two grams of morpholine and 0.5 gram of talc were added to two hundred fty cubic centimeters of water, after which the mixture was heated to 90 C. with stirring to disperse `the talc. One hundred grams of a solution of hydrogenated rubbery polybutadiene in methylcyclohexane (identical to thesolutionof Example I) was heated to about 70 C., after which two grams of oleic acid rwas added to the mixture. This polymer solution was then added to the solution of morpholine and talc in water with stirring. An additional two grams of morpholine and two grams of oleic acid were added to the resulting mixture, and :this mixture was then heated under retluxing conditions (81 C.). This heating was carried out with vigorous stirring for fifteen minutes. After this step, lthe emulsion was cooled gradually with moderate stirring to 50 C. after which the methylcyclohexane was stripped off under vacuum. This stripping was carried out within the temperature range of from 4060 C. Theemulsion, after cooling to room temperature, was divided into two approximately equal portions. One portion was divided into three aliquots. One of these aliquots was poured onto saturated sodium chloride solution, and a crumb'of coagulated polymer resulted. The second aliquot was poured onto acetone, and very small particles of polymer precipitated. The third aliquot was divided in half, and half was poured into a large excess of methanol by the method of Example I. This method gave small particles of precipitated polymer. A portion of the second half was tested by pouring methanol into the portion. This resulted in a coagulated crumblike polymer. The remainder of the second half 'was precipitated by pouring into approximately two liters of methanol, and small particles of precipitated polymer resulted; The product from this test was a tine white powder, and each particle was shown to be approximately spherical in shape when analyzed with a microscope.

It is to be noted thatin Examples l, Il, and lll that when the emulsion of rubbery polymer in water was poured into methanol with a minimum of agitation, small particles of precipitated polymer in a size range of 2 to 10 microns were obtained. With reference to Example HI, it is to be noted that the use of sodium chloride as a precipitating agent provided .a vcrumb of coagulated polymer rather than the `finely sub-divided particles of this invention. It is also to Vbe noted that in Example 'IIL a coagulated crumb-like polymer resulted when methanol was poured into the polymer in water emulsion.

Having thus described the invention by providing specic examples thereof, it is to be understood that no undue limitations or restrictions are to be drawn by reason thereof and that many modifications and variations are Within the .scope of the invention.

We claim:

l. A process for the preparation of nely sub-divided hydrogenated rubbery polymer which comprises dissolving a hydrogenated polymer selected from the group consisting of homopolymers of dienes and copolymers of styrene and butadiene, containing not more than about 30 parts of styrene byweight in a solvent, emulsifying the resulting solution with water and an oil-soluble emulsifying agent at a temperature below the softening point of the rubbery polymer, vaporizing the solvent from the emulsion at a temperature below the softening point of the "rubbery polymer and introducing the emulsion into a water-soluble polar organicprecipitating agent selected from the `group .consisting of pyridine, alkyl amines, 'alkyl alcohols and alkyl ketones in which the alkyl group contains notmore than ve carbon atoms, with a minimum of agitation'whereby finely sub-divided polymer is obtained.

2. The process of claim 1 in which the hydrogenated rubbery polymer `is .a hydrogenated `polybutadiene.

3. The process of claim l in which the hydrogenated rubberypolymer is a hydrogenated .copolymer of styrene and butadiene containing not more ,than about 30 parts of styrene by weight.

4. A process forthe preparation of nely sub-divided hydrogenated rubbery polymer which comprises dissolving a hydrogenated polymer selected from the .group consisting of homopolymers of dienes and copolymers of styrene and butadiene, containing not more than about 30 parts of styrene by weight in a solvent, emulsifying the resulting solution with water and an oil-soluble emulsifying agent Yat a temperature below the softening point of the rubbery polymer, vaporizing the solvent from the emulsion at a .temperature below the softening point of the ,rubbery polymer and introducing the emulsion onto the surface of a water-soluble vpolar organic precipitating agent selected from the group consisting of pyridine, Valkyl amines, alkyl alcohols and alkyl ketones in which the alkyl group .contains not more than tive carbon atoms, with aminimum of agitation whereby finely sub-divided polymer is obtained.

5. The process of claim 4 in which the hydrogenated rubbery polymer is hydrogenated polybutadiene.

6. The process .of claim 4in which the hydrogenated rubbery polymer is a hydrogenated copolymer of butadiene and styrene containing not more than about 30 parts of styrene by weight.

V7. A process for the ,preparation of nely sub-divided hydrogenated polybutadiene polymer containing from 0 to 50 percent unsaturation which comprises dissolving said polymer `in a solvent, emulsifying the resulting solution with water in an amount comprising at least 30 percent by "weight of'the'solution of said polymer and an oil soluble emulsifying agent at a temperature below the softening point of said polymer, vaporizing from the emulsion at a temperature below the softening point of said polymer and introducing the emulsion into a water-soluble polar organic-precipitating agent present in an amount equal to between about 5 and about 10 times the weight of the water present in said emulsion, said precipitating agent being selected from the group consisting of pyridine, alkyl amines, alkyl alcohols and alkyl ketones the alkyl group containing not more than 5 carbon atoms, with a minimum of agitation whereby finely sub-divided polymer is obtained.

8. A process for the preparation of finely sub-divided hydrogenated polybutadiene polymer containing from 0 to 50 percent unsaturation which comprises dissolving said polymer in -a solvent, emulsifying the resulting solution with water in an amount comprising at least 30 percent by weight of the solution of said polymer and an oil soluble emulsifying agent at a temperature below the softening point of said polymer, vaporizing the Solvent from the emulsion at a temperature below the softening point of said polymer and introducing the emulsion onto the surface of a water soluble polar organic precipitating agent present in an amount equal to between about 5 and about jl0`times the weight of the water present in said emulsion, said precipitating agent being selected from the group consisting of pyridine, alkyl amines, alkyl alcohols and alkyl ketones the alkyl group containing not more than 5 carbon atoms, with a minimum of agitation whereby iinely sub-divided polymer is obtained.

9. The'process of claim 8 in which the yprecipitating agent is methanol.

10. The process of claim 8 in which the precipitating agent is acetone.

No references cited.

the solvent, 

1. A PROCESS FOR THE PREPARATION OF FINELY SUB-DIVIDED HYDROGENATED RUBBERY POLYMER WHICH COMPRISES DISSOLVING A HYDROGENATED POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF DIENES AND COPOLYMERS OF STYRENE AND BUTADIENE, CONTAINING NOT MORE THAN ABOUT 30 PARTS OF STYRENE BY WEIGHT IN A SOLVENT, EMULSIFYING THE RESULTING SOLUTION WITH WATER AND AN OIL-SOLUBLE EMULSIFYING AGENT AT A TEMPERATURE BELOW THE SOFTENING POINT OF THE RUBBERY POLYMER, VAPORIZING THE SOLVENT FROM THE EMULSION AT A TEMPERATURE BELOW THE SOFTENING POINT RUBBERY POLYMER AND INTRODUCING THE EMULSION INTO A WATER-SOLUBLE POLAR ORGANIC PRECIPITATING AGENT SELECTED FROM THE GROUP CONSISTING OF PRYIDINE, ALKYL AMINES, ALKYL ALCOHOLS AND ALKYL KETONES IN WHICH THE ALKYL GROUP CONTAINS NOT MORE THAN FIVE CARBON ATOMS, WITH A MINIMUM OF AGITATION WHEREBY FINELY SUB-DIVIDED POLYMER IS OBTAINED. 